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Solid State Sciences 10 (2008) 768e775

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An optical, EPR and electrical conductivity study of blue

barium titanate, BaTiO3d
Marius Schrader a, Dirk Mienert a, Tae-Sik Oh b, Han-Ill Yoo b, Klaus Dieter Becker a,*,1
a
Institut für Physikalische und Theoretische Chemie, Technische Universität Braunschweig,
Hans-Sommer-Strasse 10, D-38106 Braunschweig, Germany
b
Seoul National University, Seoul, Korea
Received 16 February 2007; received in revised form 28 March 2007; accepted 6 April 2007
Available online 21 April 2007

Abstract

The electronic UVeVISeNIR absorption spectra of single crystalline BaTiO3d (BTO) are studied in the temperature range of 102e1173 K
in pure oxygen and at conditions of moderate and strong reduction of the material. The strongly reduced crystals are of deep blue colour. The
optical spectra of blue BTO are characterised by a strong absorption in the NIR region at around 7000 cm1, which is attributed to polaronic
defects associated with the formation of Ti3þ in the material. This assumption is supported by fits of the spectra using polaronic line shape func-
tions appropriate for disordered systems and also by the electrical conductivity of blue BTO which, in agreement with results from the optical
spectra, exhibits an activation energy of 0.20 eV. The EPR spectra of moderately reduced BTO powders show an anisotropic g-factor, which is
compatible with the optical spectrum. The temperature dependence of the band gap energy of BTO was found to be given as dEg/
dT ¼ 7.21  104 eV/K.
Ó 2007 Elsevier Masson SAS. All rights reserved.

Keywords: Barium titanate (BTO); Optical in situ spectroscopy; Small-polarons; EPR; Electrical conductivity; Band gap energy

1. Introduction As already been reported by numerous authors, reduction of

Barium titanate, BaTiO3d, is an important material with
use in a host of electronic components. It is, therefore, of great
interest to gather information about possible degradation pro-
cesses, which may occur at working conditions and may es-
sentially change certain properties of the material. In this
paper we will report mainly on the effects of chemical reduc-
tion of barium titanate (BTO). At working conditions, strong
reduction of materials may occur, e.g., in situations where
they are exposed to electrical potential gradients.
* Corresponding author. Tel.: þ49 531 3915341; fax: þ49 531 3917305.
E-mail address: k-d.becker@tu-braunschweig.de (K.D. Becker).
1
Present address during sabbatical leave: School of Physical, Environmen-
tal and Mathematical Sciences, UNSW@ADFA, Canberra, ACT 2600,
Australia.
Ti4þ containing oxides can lead to significant changes in their
optical properties due to the formation of Ti3þ ions. The most
extensively studied system in this respect is rutile, TiO2, see
e.g. Refs. [1e10]. In their recent study of the electronic ab-
sorption spectra of strongly reduced blue rutile, Khomenko
et al. [10] decomposed the strong band system in the NIR
with a maximum at around 6500 cm1 into a sum of three
components at 12,000, 7000, and 2700 cm1 with half widths
ranging between 5500 and 8400 cm1 (at 298 K). Two further
bands of much weaker intensity were observed at about 18,000
and 23,000 cm1. The whole spectrum is dominated by the ab-
sorption in the NIR, which together with the absorption edge
at 24,000 cm1 forms a minimum absorption in the blue re-
gion of the optical spectrum. This causes the observed colour
of the crystal. The origin of the complex band system in the
NIR of TiO2 was attributed to small-polaron type Ti3þeTi4þ
charge transfer processes involving Ti3þ ions on regular and

1293-2558/$ - see front matter Ó 2007 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.solidstatesciences.2007.04.011
 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775
on interstitial sites of octahedral coordination. Evidence for
the existence of titanium interstitials in strongly reduced rutile
is provided by a TEM study of Bursill and Blanchin [11]. The
two weak bands observed at 18,000 and 23,000 cm1 were
attributed by Khomenko et al. [10] to transitions to the Jahn-
Teller split upper 2Eg states of Ti3þ ions in tetragonally dis-
torted octahedral coordination.
Similar to the case of rutile, strong reduction of single crys-
talline barium titanate, BaTiO3d (BTO), also yields crystals of
deep blue colour. First mention of the strong infra-red absorp-
tion of blue BTO single crystals appears to be due to Field
et al. [12]. Further optical studies of reduced BTO are, e.g.,
due to Ikegami et al. [13,14], and Arend et al. [15]. Gerthsen
et al. [16] and Bursian et al. [17] have interpreted the reflec-
tance and the optical spectrum in the NIR, respectively, of
blue BTO in the framework of small-polaron theory. On the
other hand, Berglund and Braun [18] proposed free-carrier ab-
sorption to contribute significantly to the optical absorption of
BTO in the NIR region. It is interesting to note that many au-
thors have been aware of the fact that BTO can also be coloured
by electrochemical means, see e.g. Refs. [19,20]. In the present
study, we will report on an investigation into the origin of the
blue colour in strongly reduced BTO by using optical spectros-
copy, EPR, and electrical conductivity.
2. Experimental
Single crystals of BTO (substrate grade) grown by the top
seeded solution growth technique were obtained from MaTecK
Crystal Technology GmbH (dimensions 5  5  1 mm3). The
as-received single crystals of BTO are of faintly yellowish in
colour. To strongly reduce the crystals, they were sealed under
vacuum together with Zr or Ti metal foils in quartz vials,
Fig. 1, and annealed at 1273 K for about 6 h. To avoid any
contact of BTO with the metals, a small piece of quartz was
placed in between. This also ensures that reduction will take
place via the gas phase exclusively. The resulting oxygen par-
tial pressures were calculated using tabulated thermodynamic
data [21] for the oxide formation reaction at 1273 K, yielding
oxygen partial pressures of 5  1029 bar and 5  1035 bar
for Titanium and Zirconium foils as reducing agents,
respectively.
The optical absorption experiments on single crystals at
room temperature and at low temperatures were carried out
metal foil
BTO
quartz spacer
Fig. 1. Schematic drawing of a quartz vial used for the reduction experiments.
769
using a Perkin Elmer Lambda 900 spectrometer with an inverse
optical path [22]. Temperature dependent band gap energies
at elevated temperatures were determined from measurements
on a Perkin Elmer Lambda 9 spectrometer equipped with an
external setup for high temperature experiments [23]. The
experimental quantity accessible in the optical experiment is
the absorbance.
A ¼ logðI0 =IÞ ¼ 3cd þ AR ¼ ad þ AR ð1Þ
Here, I0 is the intensity of the incoming light and I that of
the light transmitted through the crystal. 3 (dm3 cm1 mol1),
c (mol dm3) and d (cm) represent the molar (decadic) absorp-
tion coefficient, the concentration of the absorbing species,
and the thickness of the crystal, respectively. a (cm1) denotes
the linear (decadic) absorption coefficient. AR accounts for
intensity losses due to reflection at the crystal surfaces and
is given by AR ¼ 2 logð1  RÞ, where R is the reflectivity
R ¼ ðn  1Þ2 =ðn þ 1Þ2 determined by the index of refraction n.
For optical spectroscopy at high temperature in situ condi-
tions, a custom built gas tight furnace was used allowing for
temperatures up to 1373 K with various gases or gas mixtures
[22]. The flowing mixed gases were provided by commercial
gas mixing equipment (MKS 647B); oxygen partial pressures
were monitored by an electrochemical oxygen sensor (Metro-
tec A-15-N). For the optical measurements at low tempera-
tures, a liquid nitrogen bath cryostat (Oxford Instruments
Optistat DN) was used. For optical experiments the reduced
crystals were cut into smaller slabs of the dimensions
2  2  0.31 mm3.
The electrical conductivity is measured with a precision
LCR meter (HP 4284A) by using the four wire technique
with two electrodes in the frequency range between 20 Hz and
1 kHz. Measurements were made between room temperature
and 773 K in nitrogen atmosphere for which an oxygen partial
pressure of about 5  104 bar was determined by means of
a zirconia based EMF cell integrated into the furnace. The sam-
ple temperature is measured by an S-type Pt/PtRh10 thermo-
couple, which is placed about 5 mm away from one end
of the sample. For measurements, the faces of the blue BTO sin-
gle crystal of dimension l ¼ 0.145 cm and area of 0.3  0.4 cm2
were painted with platinum paint and clamped between two
platinum electrodes.
For EPR measurements on reduced powders, polycrystal-
line BTO (99.995%, Sigma-Aldrich) was pressed into pellets
of 4 mm in diameter and annealed in a flowing CO/CO2 gas
mixture ( pO2 ¼ 1018 bar) for 1 h at 1273 K. Subsequently,
the pellets were ground to fine powders. The EPR spectra
were taken with a Bruker EMX spectrometer. Variation in tem-
perature between room temperature and 120 K was achieved
by nitrogen gas cooling.
3. Results and discussion
Strong reduction of an oxide material brings about massive
changes in its point defect inventory, notably leading to the
possible formation of anion vacancies, cation interstitials,
and electrons. In the present case, the latter will be assumed
770 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775

to be mainly localised at Ti4þ ions, causing the reduction of wavelength [nm]

Ti4þeTi3þ according to following equations: 3000 1500
120
102 K
1
OxO % O2 ðgÞ þ VO þ 2e0

ð2Þ 100
2

e0 þ TixTi %Ti0Ti ð3Þ 80

α [cm-1]
Due to lacking evidence and due to the tight packing of ions in 60

the perovskite structure [24], no formation of titanium intersti-

40
tials is assumed, which differs from the situation in oxygen de-
ficient TiO2 [10,11]. In addition to the point defects created by
20
the reactions of Eqs. (2) and (3), electrostatic interactions of
Ti3þ ions may lead to the formation of various associates ac-
0
cording to 5000 10000 15000 20000 25000
  
wavenumber [cm-1]
Ti0Ti þ VO % Ti0Ti VO
 
ð4Þ
    x Fig. 3. Optical absorption spectrum of single crystalline blue BTO at 102 K
Ti0Ti þ Ti0Ti VO % Ti0Ti VO Ti0Ti
 
ð5Þ fitted by three Gaussian peaks.

In conclusion, there are several defects, namely Ti3þ (2Eg ) 2T2g) as already been proposed by Khomenko
Ti0Ti ; ðTi0Ti VO Þ ; and ðTi0Ti VO Ti0Ti Þx involving Ti3þ, where


et al. [10] in the case of reduced titania, TiO2. In order to probe

the trapped electrons may hop amongst equivalent sites as is
indicated schematically in Fig. 2. Thus, the situation in BTO
differs from that encountered in the case of TiO2, where the
participation of interstitial Ti3þ ions had been assumed [10].
The electronic absorption spectra of single crystalline blue
BTO at 102 K and 298 K are shown in Figs. 3 and 4, respec-
tively. Both spectra are dominated by a broad absorption region
in the NIR range. In a first attempt to fit the experimental spec-
tra, Gaussian line shape functions have been used. Motivated
by the appearance of the total absorption band shape, we
have attempted fits using three Gaussians. By this strategy,
good fits could be obtained, see Figs. 3 and 4, yielding a strong
peak at 6000 cm1 (5700 cm1), a broad absorption band
at 11,800 cm1 (11,600 cm1), and a weak absorption at
24,600 cm1 (20,800 cm1) at 102 K (298 K), see Table 1.
Band positions and band widths are in remarkable correspon-
dence with the results obtained by Khomenko et al. [10] for
blue TiO2, see Section 1. Generally, we observe in the optical
spectra a shift of the absorption peaks to higher energies with
decreasing temperature and a sharpening of the line shapes,
which both is in agreement with general expectations, Table 1.
The absorption of small intensity observed around
23,000 cm1 is attributed to a spin-allowed dd-transition on
more deeply into the nature of this transition, its oscillator
strength is calculated according to following equation:
f z4:6  109 3max D~n1=2 ð6Þ
which is valid for bands of Gaussian shape [25]. Here,
3max ¼ Amax/cd ¼ amax/c (dm3 cm1 mol1) represents the mo-
lar decadic absorption coefficient at the band maximum and
~n1=2 (cm1) the full width of the Gaussian band shape at
half maximum (FWHM). To get an order of magnitude esti-
mate of the concentrations of Ti3þ ions, we have used data
on the nonstoichiometry parameter d of BaTiO3d according
to Yoo and coworkers [26] and literature cited therein. For
1273 K, a value of the order of d ¼ 5  102 at pO2 z 1030
bar is estimated which amounts to c(Ti3þ) ¼ 2d/Vm z 2.5
mol dm3, where the molar volume of Vm(BaTiO3) ¼ 40 cm3
has been used. It must be admitted, however, that this d-value
wavelength [nm]
3000 1500
120
298 K
100
80
α [cm-1]

60

40

e- e- e- 20

0
e-
5000 10000 15000 20000 25000
(a) (b) wavenumber [cm-1]

Fig. 2. (a) Free polaronic motion of electrons, (b) localised motion of electrons Fig. 4. Optical absorption spectrum of single crystalline blue BTO at 298 K
trapped at anion vacancies. fitted by three Gaussian peaks.
 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775 771

Table 1
Spectroscopic parameters, peak positions and full width at half maximum 2000
(a) experimental data
(FWHM), derived from analysis of experimental data by a fit using three simulation
Gaussian lines 1500

Fit 1 2 3 1000

intensity
1
102 K, 3 Gaussians Position [cm ] 24,570 11,820 5980
FWHM [cm1] 4995 14,245 7010 500
1
298 K, 3 Gaussians Position [cm ] 20,780 11,610 5670 0
FWHM [cm1] 5190 10,950 7425
-500

is derived from an extrapolation of existing data by about 10 -1000

orders of magnitude in oxygen partial pressure which makes 3280 3300 3320 3340 3360 3380 3400 3420
this estimate very uncertain. It is also to be noted that the magnetic field [G]
evaluation of nonstoichiometry is based on the assumption
Fig. 6. Experimental and theoretical ( gt ¼ 1.973, g ¼ 1.952) EPR spectra of
that the extremely low oxygen activities are really attained in reduced BTO powder at 120 K.
the equilibration process, see Section 2. In that far, the above
d-value represents an upper limit. From the estimated Ti3þ con-
centration, amax z 5 cm1, Figs. 3 and 4, and the band width, and
Table 1, we obtain an oscillator strength of f z 4.6  105.
gt ¼ ge  2ðl=E1 Þ ð7bÞ
This value is characteristic for spin-allowed, Laporte forbidden
dd-transitions [27] and, thus, confirms the present assignment
Here, l is the spin-orbit interaction parameter and Ei is elec-
of the band around 23,000 cm1.
tronic excitation energies of Ti3þ ions from the dxy ground
The presence of Ti3þ in reduced BTO is also confirmed by
state to excited states. In view of the above interpretation of
EPR. Fig. 5 shows a selection of temperature dependent spec-
the optical band in the UV range we can make the assignment
tra of a BTO powder sample that was reduced at 1273 K and
of E2 (dxy /dx2 y2 ) ¼ 24,570 cm1 at 100 K, Table 1. Using
pO2 z 1018 bar for 1 h. As seen, the anisotropic EPR spec-
l ¼ 154 cm1 for Ti3þ, Eq. (7a) yields a value of g ¼ 1.952,
trum observed at low temperature decreases in intensity and
which is in excellent agreement with the EPR experiment at
looses its characteristic features with increasing temperatures.
120 K. On the other hand, the above experimental value of
The EPR spectrum at 120 K is shown in Fig. 6. It exhibits
gt points to an excitation energy E1 ðdxy /dyx ; dzx Þ of about
a line shape that can very well be described by an anisotropic
10,500 cm1. Thus, a spin-allowed dd-transition may also
g-factor with g ¼ 1.952 and gt ¼ 1.973. The theoretical line
contribute to the absorption in the NIR region. However, due
shape function for these parameters is also shown in the graph
to the expectedly small intensity of such a transition, no at-
for comparison. For a tetragonally distorted d1 ion, the g-factor
tempt will be made in the present case to resolve this band
differs from the free electron value of ge ¼ 2.0023 and is an-
in the presence of the strong NIR absorption. Indeed, such
isotropic due to a small contribution of orbital angular mo-
a second contribution with the expected small oscillator
mentum yielding [28]
strength has been observed in the case of blue TiO2 [10].
As already indicated above, rapid electron hopping
gk ¼ ge  8ðl=E2 Þ ð7aÞ amongst equivalent sites may occur in reduced BTO, see
Fig. 2, which can be considered as small-polaron hopping pro-
cesses. In that case, optical absorption bands arise due to the
2000 charge transfer processes associated with the polaronic motion
120 K
of the electrons. For unrestricted small-polaron hopping in cu-
1600
bic symmetry, Reik [29] has given the following simplified ex-
1200 pression for the optical conductivity.
800
1  expðZu=kTÞ
intensity

sðuÞ ¼ sð0Þ
400 Zu=2kT
 
0 exp  ðZu  4Em Þ2 =16Em kT expðEm =kTÞ ð8Þ
-400
298 K
Here Zu denotes the photon energy, sð0Þ the electrical dc con-
-800 ductivity due to small-polaron hopping, and Em the thermal
-1200 hopping energy of the small-polaron. Eq. (8) as well as
3200 3250 3300 3350 3400 3450 3500 more elaborate expressions of this type [5,30e32] represent
magnetic field [G]
slightly asymmetric Gaussian line shapes with the maximum
Fig. 5. EPR spectra of reduced BTO powder as a function of temperature at Zumax z4Em . The frequency dependent optical conductivity
(120  T/K  298). is directly related with the optical absorption coefficient by
772
aðuÞ ¼ sðuÞlogðeÞ=nc30 , where n is the index of refraction, c
the speed of light, and 30 the permittivity of free space. There-
fore, the Gaussian fits displayed in Figs. 3 and 4 represent rea-
sonable first approximations to the case of polaron induced
optical absorption. Consequently, the fits to the NIR absorp-
tion line shape yielding maxima at about Zumax z0:72 eV
Table 1, indicate an activation energy for small-polaron hop-
ping of Em z 0.2 eV.
The spectroscopic investigation into blue BTO is comple-
mented by a study of the electrical conductivity of single crys-
talline blue BTO. Measurements have been made between
room temperature and 773 K in a nitrogen atmosphere.
Fig. 7 shows the Arrhenius plot of the data according to fol-
lowing equation:
 
Ea
sT ¼ S0 exp  ð9Þ
kT
yielding an activation energy of Ea ¼ 0.20  0.02 eV and
S0 z 3  102 U1 cm1 K. As it turned out in our attempts
to re-oxidise the blue BTO single crystals, re-oxidation of
this material is very sluggish. Accordingly, after the conduc-
tivity measurements in the above limited temperature range,
the crystal was still blue in colour indicating that the concen-
trations of mobile electrons can be considered in good approx-
imation as constant and, thus, as temperature independent. In
this case, the apparent activation energy Ea of electrical con-
duction corresponds to the migration enthalpy of the charge
carriers. With Ea ¼ Em z 0.20 eV from conductivity and
Zumax ¼ 0:71 eV (5700 cm1) from optical spectroscopy, it
is seen that the relation Zumax z4Em characteristic for small-
polaron hopping, Eq. (8), is fulfilled in the present case within
experimental error. We consider this coincidence as strong ev-
idence for the conclusion that the electronic absorption of blue
BTO in the NIR is due to small-polaron hopping of electrons.
The other absorption maximum in the NIR region occurs at
about 1.45 eV. In this case, the comparison with electrical
T [K]
1000 800 600 400
2,0
1,5
log(σT/K Ω -1cm -1)
1,0
0,5
0,0
-0,5
0,0010 0,0015 0,0020 0,0025
1/T [K-1]
Fig. 7. Arrhenius plot of the electrical conductivity of single crystalline blue
BTO between room temperature and 773 K.
M. Schrader et al. / Solid State Sciences 10 (2008) 768e775
conductivity is not favourable. We are, therefore, led to the
conjecture that several hopping processes may contribute to
optical absorption in the NIR, which apparently do not all con-
tribute fully to the macroscopic transport of charge. According
to our analysis, the hopping process that dominates the electri-
cal conductivity of blue BTO is associated with the absorption
around 6000 cm1 (0.75 eV).
Using Eqs. (8) and (9) and the above relation between s(u)
and a, the absorption coefficient can be written as
2kS0 log e 1  expðZu=kTÞ
aðuÞ ¼
nc30 Zu
 2 
exp  ðZu  4Em Þ =16Em kT ð10Þ
Thus, a can be calculated from the conductivity parameters
and compared with the optical experiments, Figs. 3 and 4. In
agreement with experiment Eq. (10), indeed, predicts almost
temperature independent values for the maximum absorption
coefficient as long as Zu > kT. Using the above conductivity
parameters (S0, Em) and an index of refraction of n ¼ 2.4 [33],
the absorption peak around 6000 cm1 is calculated to take
a maximum value of about 10 cm1 at 100 K as well as at
300 K. However, experimental values are found to range at
amax z 60 cm1, Figs. 3 and 4. To this discrepancy in the
maximum values the following causes may contribute: (i)
the approximate nature of Eq. (8), also see below, and/or (ii)
retarding effects, e.g. polarization, on the conductivity mea-
surements reducing the experimental conductivity values.
There is, however, one more flaw in the comparison of the
theoretical small-polaron line shape and experimental spectra:
the FWHM width of the theoretical shape function predicted
by Eqs. (8) and (10) at 300 K amounts to 0.50 eV if a hopping
energy Em of 0.20 eV is assumed. This is close to the width of
a symmetrical Gaussian exp½ðZumax  ZuÞ2 =16Em kT pos-
sessing a FWHM of 8(EmkT ln 2)1/2, which yields a width of
0.48 eV. Thus, the width of the theoretical line shape function
given by Eqs. (8) and (10) is significantly smaller than that of
the experimental spectrum at 300 K, which is about 0.90 eV,
Table 1. The discrepancy is much larger at 102 K. Even
a more refined version of Eq. (8) [30,31] yields only
a FWHM value of 0.60 eV at 300 K. In addition to this, also
blue BaTiO3 the approximate T1/2 dependence of the FWHM predicted by
single crystal Eqs. (8) and (10) is not observed. We consider that one of
N2atmosphere
the reasons for these deficiencies may be due to the high de-
linear fit
Q = 0.202(16) eV
gree of electronic and ionic disorders of the material as sug-
gested by the above estimate of the stoichiometry parameter
d. This will give rise to polaronepolaron interactions, which
are not accounted for in the derivation of Eq. (8) and its var-
iants [5,30e32].
Bryksin [34,35] has treated the absorption of light in disor-
dered systems with hopping conduction near the Fermi level.
In this treatment, the density of states of electrons is intro-
duced and accounted for by a distribution function
0,0030 0,0035 0,0040
P(E ) w exp(E2/2G2). From his treatment, a line shape is pre-
dicted which can be significantly broadened and highly asym-
metric. The optical conductivity can be approximated by
[34,35]
 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775 773

" #
2
m2 ðZu  4Em Þ 120 298 K
sðuÞzC exp  2  for Zu  a ð11aÞ
G 16Em kT
100

" # 80
2
m2 ðZu  4Em  mÞ

α [cm-1]
sðuÞzC exp   for a < Zu  b
2G2 16Em kT þ 2G2 60

ð11bÞ 40

" # 20
2
ðZu  4Em Þ
sðuÞzC exp  for Zu  b ð11cÞ
16Em kT þ 4G2 0

0,5 1,0 1,5 2,0 2,5 3,0 3,5

where C is a prefactor and a and b are given by photon energy [eV]

4Em ð1  ð2mkT=G2 ÞÞ and 4Em ð1 þ ð2mkT=G2 ÞÞ þ 2m, respec-
tively. m represents the Fermi energy of the Gaussian distribu-
tion function P(E ) as measured from its centre. The maximum
of the polaronic line shape function according to Eq. (11) is
located at Zumax z4Em þ m with its width given by
pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2  
FWHM ¼ 4Em kT þ G2 2G2 ln 2 þ m2
G
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
tude, the line shape function Eq. (11) can also very well ac-
 
þ 4Em kT 2G2 ln 2  m2
The fit of Eq. (11) to the experimental spectrum in the NIR
part of the spectrum is shown in Figs. 8 and 9. In contrast to
the Gaussian fits of Figs. 3 and 4, the contribution at around
6400 cm1 now provides the dominating contribution to the
absorption in the NIR. This is mainly due to the width param-
eter G of the density function of states which takes values in
the range of 0.3 eV, Table 2. In addition to the small-polaron
line shape function peaking at 6400 cm1, the fit contains
a second polaron band of smaller integral intensity at around
14,000 cm1 as well as a Gaussian band at around
19,000 cm1, Table 2. In keeping with the discussion given
in the context of Figs. 3 and 4, the latter band is attributed
to dd-transitions on the Ti3þ ions. To avoid ambiguity, also
in the present case we will not attempt to include a further
Gaussian band in the fit though this may be justified on basis
Fig. 9. Optical absorption spectrum of single crystalline blue BTO at 298 K
fitted by two polaronic line shape functions, Eq. (11), and one Gaussian peak.
of the anisotropic EPR spectra. The presence of a second po-
laron band at higher energies clearly indicates the presence of
 several types of polaron processes, as can easily be understood
by referring to Fig. 2. With G-values of this order of magni-
ð12Þ count for the reduced temperature dependence of the
experimental width of the polaron band. Using typical values
of Em ¼ 0.18 eV, G ¼ 0.30 eV, and m ¼ 0.05 eV one obtains
a ratio FWHM(300 K)/FWHM(100 K) ¼ 1.19, Eq. (12), which
compares reasonably well with the experimental value of 1.06,
see Table 2.
Finally, it is in order to comment on an obvious alternative
to the fit strategy of the electronic spectra of blue BTO. As
may be recognized from the spectra shown in Figs. 8 and 9,
alternative fits of comparable quality can be obtained if the ab-
sorption around 14,000 cm1 is fitted by a Gaussian function.
This would mean that this band is assumed to be due to a dd-
transition on Ti3þ. However, such transitions are spin-allowed
and Laporte forbidden. In thus, their oscillator strength should
be close to that of the band around 21,000 cm1. Indeed, in the
case of blue TiO2, Khomenko et al. [10] observed two transi-
tions of virtually identical oscillator strength in the VIS region.
However, in the present case, a Gaussian band around

120 102 K
Table 2
100 Spectroscopic parameters, peak positions, full width at half maximum
(FWHM), hopping energies Em, G-values, and Fermi energy m derived from
80 analysis of experimental data by fits using two polaronic line shape functions
according to Bryksin (B) [34,35], Eq. (11), and one Gaussian (G) peak
α [cm-1]

60
Fit G B1 B2

40 102 K Position [eV] 2.76 1.75 0.79

2 Bryksin functions FWHM [eV] 0.66 1.01 0.75
20 1 Gaussian Em [eV] 0.39 0.18
G [eV] 0.33 0.28
0 m [eV] 0.15 0.07

0,5 1,0 1,5 2,0 2,5 3,0 3,5

298 K Position [eV] 2.42 1.71 0.75
2 Bryksin functions FWHM [eV] 0.66 0.97 0.79
photon energy [eV] 1 Gaussian Em [eV] 0.39 0.18
G [eV] 0.31 0.31
Fig. 8. Optical absorption spectrum of single crystalline blue BTO at 102 K
m [eV] 0.15 0.03
fitted by two polaronic line shape functions, Eq. (11), and one Gaussian peak.
774 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775

14,000 cm1 would possess a more than 10 times larger inte- 7,5
gral intensity than the band at 21,000 cm1. For this reason, temperatures (from right to left)
298 K
the alternative fit strategy is dismissed, which at the same

A2*wavenumber2 [109cm-2]
473 K T
time strengthens the conclusion that (at least) two different po- 673 K
5,0
laronic processes appear to exist in blue BTO. This, however, 873 K
can easily rationalised in view of the possible processes sche-
matically indicated in Fig. 2.
To obtain further insight into the nature of the absorption 2,5
phenomena observed in the NIR region, an estimate of the os-
cillator strength was made of the band peaking at 6300 cm1.
Using amax z 80 cm1, the above estimated concentration of
0,0
electrons, and a width of the polaron band of FWHM z
7000 cm1, an f-number of the order of 103 is obtained, 10000 15000 20000 25000
Eq. (6). This value is much smaller than what is expected wavenumber [cm-1]
for charge transfer processes, for which oscillator strengths
Fig. 10. Determination of band gap energies of single crystalline BTO for sev-
are of the order of 0.01e0.1 [27,36]. This discrepancy may eral selected temperatures (in air).
be resolved in part by considering (i) that in view of the above
remarks on the estimate of the stoichiometry parameter
d achieved in the reduction process, the oscillator strength following temperature dependence of the band gap energy of
determined here may be regarded as a lower limit to the true BTO
oscillator strength of this transition and (ii) that different elec-
tronic defects are created in reduced BTO. In addition to the Eg ðTÞ=eV ¼ 7:21  104 ðT=KÞ þ 3:05 eV ð14Þ
ones already displayed in Fig. 2, also colour centre type de-
Thus, at room temperature the band gap energy of BTO is
fects VO ¼ ðVO þ e0 Þ or VO ¼ ðVO þ 2e0 Þ may be formed.
found to be Eg ¼ 2.83 eV. This is in reasonable agreement with
However, their individual concentrations, and especially those
the literature where values for Eg have been reported ranging
of electrons involved in unrestricted three dimensional small-
from 2.9 eV (powder) to 3.2 eV (single crystal, light perpen-
polaron hopping processes, are not known. In conclusion, the
dicular to ferroelectric c-axis) [39e42]. The fact that the pres-
present discussion seems to suggest that only a small fraction
ent value is at the low end of the published data for Eg may
of the electrons created due to chemical reduction are involved
indicate that there could be an additional absorption in the
in the polaronic optical absorption process associated with the
edge region, probably due to an unknown impurity in the crys-
electronic conductivity of the material.
tal investigated.
In contrast to interpretation given in the present contribu-
tion, Berglund and Braun [18] argue that free carriers contrib-
ute significantly to the absorption in the NIR. Their conclusion 4. Conclusions
is mainly based on the observation that the high-energy tail of
the NIR absorption possesses a power-law dependence on pho- The optical spectra of strongly reduced, blue barium tita-
ton energy. However, as demonstrated by Figs. 8 and 9, the nate (BTO) at room temperature (298 K) and at low tempera-
present interpretation involving small-polaron hopping in a dis- tures (102 K) were found to be dominated by a region of
ordered system can account almost perfectly for the experi- strong absorption in the NIR. Because Ti4þ ions exhibit no
mental line shapes.
With increasing temperatures, the optical spectrum of BTO
3,0
is dominated by the significant shift of the absorption edge to
2,9
lower energies. From the absorbance A in the edge region, the
band gap energies Eg can be calculated according to Tauc’s 2,8

equation [37] 2,7

 m 2,6
Eg[eV]

AZuf Zu  Eg ð13Þ 2,5

2,4
where the exponent m depends on the nature of the observed
2,3
transition. According to Cardona [38], the optical absorption
edge in BTO is due to an allowed direct transition, for which 2,2
case m ¼ ½. By plotting A2 ðZuÞ2 versus photon energy Zu, the 2,1
band gap energies can be obtained from extrapolation of the 2,0
linear part of the plot to the x-axis. This is shown in Fig. 10 200 400 600 800 1000 1200
T [K]
for several selected temperatures for measurements performed
in air. The Eg values thus derived decrease linearly with in- Fig. 11. Temperature dependent band gap energies of BTO fitted by linear
creasing temperature, Fig. 11. Linear regression yields the regression (in air).
 M. Schrader et al. / Solid State Sciences 10 (2008) 768e775
optical absorption in the VISeNIR region and because the
Ti3þ ions, associated with the reduction of BTO, are expected
to exhibit the simple spectrum of d1 ions, this finding may ap-
pear surprising at first sight. In agreement with similar obser-
vations in strongly reduced blue TiO2, the absorption is
attributed to hopping processes of small-polarons.
In the spirit of this assumption, the optical spectra have
been analysed using Gaussian line shape functions, which rep-
resent an approximation to the model of free, small-polarons at
high dilution. Indeed, the position of maximum absorption of
the NIR band and the activation energy Em for electrical con-
duction is found to obey the relation Zumax z4Em which is
usually considered as characteristic for small-polaron hopping
processes. However, it could be shown that this model is inter-
nally not consistent and insufficient to describe the experimen-
tal spectra. On the other hand, analysis of the anisotropic line
shape of the EPR spectra yields g-factors, which confirm the
presence of Ti3þ ions on distorted octahedral sites. The EPR
data are also fully compatible with an excitation energy ob-
served in the visible part of the optical spectra.
In a second approach, considered more realistic in the pres-
ent context of a strongly reduced and disordered material, po-
laronic line shape functions according to Bryksin [34,35] have
been used to fit the experimental spectra. Bryksin has treated
the absorption of light in disordered systems with hopping
conduction near the Fermi level. In this treatment, spectral
line shapes of pronounced asymmetry were derived, which is
in agreement with experiments, and the slightly changed rela-
tion Zumax z4Em þ m [34,35]. The results obtained from the
consistent fits to the optical spectra and from electrical con-
ductivity measurements (Em z 0.20 eV) are in full agreement
with this latter relation. In conclusion, the optical absorption in
the NIR, which is responsible for the blue colour of strongly
reduced BTO, is attributed to small-polaron hopping of elec-
trons of Ti3þeTi4þ charge transfer type and gives evidence
of the strongly disordered nature of the material.
The absorption edge of single crystalline BTO was found to
exhibit a significant shift with temperature, indicating a corre-
sponding temperature dependence of the band gap energy Eg.
The analysis of the data using Tauc’s equation yields a linear
decrease of Eg from 2.83 eV at room temperature to 2.26 eV at
1073 K with a temperature dependence of dEg/dT ¼ 7.21 
104 eV/K.
Acknowledgement
One of the authors (K.D.B.) would like to thank Prof. S.
Campbell and the School of PEMS for their hospitality during
his Sabbatical stay at UNSW@ADFA, Canberra, Australia.
775
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